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タイトル: Efficient synthesis and hydrolysis of cyclic oxalate esters of glycols
著者: Itaya, Taisuke
Iida, Takehiko
Gomyo, Yasuko
Natsutani, Itaru
Ohba, Masashi link image
大場, 正志
発行日: 2002年 3月
出版社(者): 日本薬学会
雑誌名: Chemical and Pharmaceutical Bulletin
ISSN: 0009-2363
巻: 50
号: 3
開始ページ: 346
終了ページ: 353
キーワード: 1,1′-oxalyldiimidazole
1,4-dioxane-2,3-dione hydrolysis
Glycol cyclocondensation
Oxalate hydrolysis kinetics
Oxalyl chloride
Stereoelectronic effect
抄録: Based on the mechanism postulated for the formation of the cyclic carbonates 3 in the reactions of glycols 1 with oxalyl chloride in the presence of triethylamine, we present here three efficient syntheses of the cyclic oxalates 2 of various glycols 1 by controlling the formation of 3: replacement of the base by pyridine markedly diminishes yields of 3 in all reactions, realizing dramatic reversals of the product ratios in the reactions with the (R*,R*)-compounds 1g-i, q, r and pinacol (1k); although considerable amounts of the oxalate polymers are formed in the reactions with some (R*,S*)-glycols, this drawback can be removed by the use of 2,4,6-collidine instead of pyridine; 1,1′-oxalyldiimidazole is useful for the synthesis of two selected cyclic oxalates 2e, f. The cyclic oxalates 2 other than trisubstituted and tetrasubstituted ones were found to be very reactive: kinetic studies on the hydrolysis of 1,4-dioxane-2,3-dione (2a) as well as its mono- and some selected 5,6-disubstituted derivatives 2 have revealed that they undergo hydrolysis 260-1500 times more rapidly than diethyl oxalate (12) in acetate buffer-acetonitrile (pH 5.69) at 25°C. Although the cyclic oxalate 2l from cis-1,2-cyclopentanediol (1l) was 1.5 times more reactive than 2a, it has been shown with other substrates that increasing number of the alkyl substituents decreases the rate of hydrolysis. On the contrary, the phenyl group was found to have somewhat accelerative effect. © 2002 Pharmaceutical Society of Japan.
DOI: 10.1248/cpb.50.346
URI: http://hdl.handle.net/2297/7561
関連URI: http://www.jstage.jst.go.jp/article/cpb/50/3/50_346/_article/-char/en
資料種別: Journal Article
版表示: publisher
出現コレクション:2.査読済論文(薬)

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